EP1273436A1 - Tubes et tuyauterie brillante - Google Patents

Tubes et tuyauterie brillante Download PDF

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Publication number
EP1273436A1
EP1273436A1 EP01202577A EP01202577A EP1273436A1 EP 1273436 A1 EP1273436 A1 EP 1273436A1 EP 01202577 A EP01202577 A EP 01202577A EP 01202577 A EP01202577 A EP 01202577A EP 1273436 A1 EP1273436 A1 EP 1273436A1
Authority
EP
European Patent Office
Prior art keywords
tubes
high gloss
pipes
metallocene
sheets
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP01202577A
Other languages
German (de)
English (en)
Inventor
Philippe Marechal
Eric Maziers
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Total Research and Technology Feluy SA
Original Assignee
Atofina Research SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Atofina Research SA filed Critical Atofina Research SA
Priority to EP01202577A priority Critical patent/EP1273436A1/fr
Priority to ES02751113T priority patent/ES2269737T3/es
Priority to AT02751113T priority patent/ATE337175T1/de
Priority to PCT/EP2002/007491 priority patent/WO2003004207A2/fr
Priority to DE60214189T priority patent/DE60214189T2/de
Priority to PT02751113T priority patent/PT1409245E/pt
Priority to US10/483,004 priority patent/US20040241362A1/en
Priority to JP2003510208A priority patent/JP2004533375A/ja
Priority to AU2002354708A priority patent/AU2002354708A1/en
Priority to EP02751113A priority patent/EP1409245B1/fr
Priority to DK02751113T priority patent/DK1409245T3/da
Priority to CNB028158016A priority patent/CN100421929C/zh
Priority to KR1020047000006A priority patent/KR100937461B1/ko
Publication of EP1273436A1 publication Critical patent/EP1273436A1/fr
Priority to US12/332,069 priority patent/US20090136699A1/en
Withdrawn legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L2201/00—Special arrangements for pipe couplings
    • F16L2201/40—Special arrangements for pipe couplings for special environments
    • F16L2201/44—Special arrangements for pipe couplings for special environments sterile

Definitions

  • This invention is related to the production of high gloss sheets, pipes, tubes or connector joints and in particular to the production of high gloss tubes formed of polyethylene.
  • High gloss high density polyethylene has been used: it is characterised by a very narrow molecular weight distribution that is typically inferior to 8.
  • the molecular weight distribution can be completely defined by means of a curve obtained by gel permeation chromatography.
  • the molecular weight distribution (MWD) is more simply defined by a parameter, known as the dispersion index D, which is the ratio between the average molecular weight by weight (Mw) and the average molecular weight by number (Mn).
  • the dispersion index constitutes a measure of the width of the molecular weight distribution. It is known that a resin of narrow molecular weight distribution will produce plastic articles of very high gloss but simultaneously, that such resin will be very difficult to process and will be characterised by very poor mechanical properties. It has also been observed that said resins have poor mechanical properties, particularly, a very low environmental stress crack resistance (Modern Plastic International, August 1993, p. 45).
  • Low density polyethylene (LDPE) and polyethylene vinyl acetate (EVA) copolymers are used to prepare articles with very smooth surface finish and thus high gloss but they suffer from a lack of rigidity, thereby requiring thick walls if used for pressurised fluids.
  • the polyethylene materials that offer high rigidity are characterised by a fairly rough surface resulting from the surface crystallisation of the polymer. The articles produced with these polymers thus have a mat finish.
  • HDPE high density polyethylene
  • high gloss plastic articles comprise an internal layer including a polyolefin and an external layer including a styrenic component containing from 40 to 85 wt% of styrene, based on the weight of the external layer, as disclosed for example in European Patent Application n° 00201155.9.
  • An aim of the present invention is to produce plastic sheets or pipes or tubes or connector joints that offer simultaneously the desired glossy appearance and a high rigidity.
  • the present invention provides single layer or multi-layer plastic sheets or pipes or tubes or connector joints, for which the external layer consists essentially of a metallocene-produced polyethylene having a density of from 0.910 g/cm 3 , preferably from 0.925 g/cm 3 , up to 0.966 g/cm 3 , or up to homopolymer densities, and a melt index MI2 of from 0.001 to 20 g/10min, preferably 0.2 to 5 g/10 min, and most preferably from 0.5 to 2.5 g/10 min, for extrusion blow moulding, and of from 0.1 to 500 g/10 min, preferably from 0.7 to 70 g/10 min for injection blow moulding.
  • the external layer consists essentially of a metallocene-produced polyethylene having a density of from 0.910 g/cm 3 , preferably from 0.925 g/cm 3 , up to 0.966 g/cm 3 , or up to homopolymer densities, and a melt index
  • the density of the polyethylene is measured at 23 °C using the procedures of ASTM D 1505.
  • the melt index MI2 is measured using the procedures of ASTM D 1238 at 190°C using a load of 2.16 kg.
  • the high load melt index HLMI is measured using the procedures of ASTM D 1238 at 190 °C using a load of 21.6 kg.
  • the external layer is prepared with a metallocene-produced polyethylene resin
  • the inner layer(s) is(are) prepared with any one of the known catalysts, such as a chromium or a Ziegler-Natta or a metallocene catalyst, said metallocene catalyst being either the same as or different from the metallocene catalyst used to prepare the external layer.
  • EP-A-0,291,824, EP-A-0,591,968 and US-A-5,310,834 each disclose mixed catalyst compositions, incorporating chromium-based catalysts, for the polymerisation of polyethylene.
  • the HDPE can be produced using a conventional Ziegler-Natta catalyst or a supported Ziegler-Natta catalyst comprising metallocene sites such as described in EP-A-0,585,512.
  • the HDPE can further be polymerised with a metallocene catalyst capable of producing a mono- or bi- or multimodal distribution, either in a two step process such as described for example in EP-A-0,881,237, or as a dual or multiple site catalyst in a single reactor such as described for example in EP-A-0,619,325.
  • a metallocene catalyst capable of producing a mono- or bi- or multimodal distribution, either in a two step process such as described for example in EP-A-0,881,237, or as a dual or multiple site catalyst in a single reactor such as described for example in EP-A-0,619,325.
  • Any metallocene catalyst known in the art can be used in the present invention. It is represented by the general formula: I.
  • Cp m MR n X q
  • M is a group 4b, 5b or 6b transition metal
  • R is a hydrocarbyl group or hydrocarboxy having from 1 to 20 carbon atoms
  • X is a halogen
  • R" s (C 5 R' k ) 2 MQ' wherein (C 5 R' k ) is a cyclopentadienyl or substituted cyclopentadienyl, each R' is the same or different and is hydrogen or a hydrocarbyl radical such as alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radical containing from 1 to 20 carbon atoms or two carbon atoms are joined together to form a C 4 -C 6 ring, R" is a C 1 -C 4 alkylene radical, a dialkyl germanium or silicon or siloxane, or a alkyl phosphine or amine radical bridging two (C 5 R' k ) rings, Q is a hydrocarbyl radical such as aryl, alkyl, alkenyl, alkylaryl, or aryl alkyl radical having from 1-20 carbon atoms, hydrocarboxy radical having 1-20 carbon atoms or hal
  • metallocenes used in the present invention one can cite among others ethylene bis-(tetrahydroindenyl) zirconium dichloride, ethylene bis-(indenyl) zirconium dichloride or bis-(n-butylcyclopentadienyl) zirconium dichloride, mono-, bi- or tri-substituted, as disclosed for example in EP-A-870,048.
  • the metallocene may be supported according to any method known in the art.
  • the support used in the present invention can be any organic or inorganic solids, particularly porous supports such as talc, inorganic oxides, and resinous support material such as polyolefin.
  • the support material is an inorganic oxide in its finely divided form.
  • An active site must be created by adding a cocatalyst having an ionising action.
  • alumoxane is used as cocatalyst during the polymerization procedure, and any alumoxane known in the art is suitable.
  • the preferred alumoxanes comprise oligomeric linear and/or cyclic alkyl alumoxanes represented by the formula : for oligomeric, linear alumoxanes and for oligomeric, cyclic alumoxanes, wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C 1 -C 8 alkyl group and preferably methyl. Methylalumoxane is preferably used.
  • one or more aluminiumalkyl represented by the formula AIR x are used wherein each R is the same or different and is selected from halides or from alkoxy or alkyl groups having from 1 to 12 carbon atoms and x is from 1 to 3.
  • Especially suitable aluminiumalkyl are trialkylaluminium, the most preferred being triisobutylaluminium (TIBAL).
  • the metallocene catalyst utilised to produce a polyethylene can be used in gas, solution or slurry polymerisation.
  • the polymerization process is conducted under slurry phase polymerization conditions.
  • the polymerisation temperature ranges from 20 to 125°C, preferably from 60 to 105°C and the pressure ranges from 0.1 to 10 Mpa, preferably from 2 to 6.5 Mpa, for a time ranging from 10 minutes to 4 hours, preferably from 0.3 and 2.5 hours, most preferably from 0.5 to 1 hour.
  • the polymerization reaction be run in a diluent at a temperature at which the polymer remains as a suspended solid in the diluent.
  • a continuous loop reactor is preferably used for conducting the polymerisation. Multiple loop reactors can also be used for polymerisation.
  • the average molecular weight is controlled by adding hydrogen during polymerisation.
  • the relative amounts of hydrogen and olefin introduced into the polymerisation reactor are from 0.001 to 15 mole percent hydrogen and from 99.999 to 85 mole percent olefin based on total hydrogen and olefin present, preferably from 0.2 to 3 mole percent hydrogen and from 99.8 to 97 mole percent olefin.
  • the density of the polyethylene is regulated by the amount of comonomer injected into the reactor; examples of comonomer which can be used include C3-C22 n-olefins or non conjugated diolefins among which the preferred are: 1-olefins, butene, hexene, octene, 4-methyl-pentene, and the like, the most preferred being hexene.
  • the densities of the polyethylenes required for preparing the high gloss sheets, tubes or pipes of the present invention range from 0.910 g/cm 3 , preferably from 0.925 g/cm 3 up to 0.966 g/cm 3 , or up to homopolymer densities.
  • the melt index of polyethylene is regulated by the amount of hydrogen injected into the reactor.
  • the melt indexes useful in the present invention range from 0.01 g/10 min to 20 g/10 min, preferably from 0.2 to 5 g/10 min and most preferably from 0.5 to 2.5 g/10 min.
  • the polyethylene resin used in the present invention can be prepared with either a single site metallocene catalyst or with a multiple site metallocene catalyst and it has therefore either a monomodal or a bimodal molecular weight distribution.
  • the molecular weight distribution is of from 2 to 20, preferably, of from 2 to 7 and more preferably of from 2 to 5.
  • polyethylene resins produced in accordance with the above-described processes have physical properties making them particularly suitable for use as blow moulding grade polyethylenes.
  • the metallocene polyethylene resins are used in the present invention for manufacturing high gloss plastic sheets or pipes or tubes.
  • the high gloss tubes or pipes of the present invention preferably have a diameter of from 0.5 to 250 mm. Said tubes or pipes are used for various applications:
  • the sheets, tubes and pipes can be manufactured by any method known in the art such as:
  • fluoroelastomer in the resin allowing for very low transformation temperatures of from 140 to 180 °C, preferably, around 160 °C. Such temperatures are 30 to 40 °C lower than the transformation temperature normally used.
  • the external layer is a metallocene-produced polyethylene and the internal layer is a polyethylene produced by any conventional method.
  • the external layer represents from 5 to 14 %, preferably about 10 %, of the total wall thickness.
  • the plastic tubes of the present invention are characterised by a very high gloss, as measured using the method of ASTM D 2457-90 standard test and a low haze as measured by the method of ASTM D 1003-92 standard test.
  • the environmental stress crack resistance is measured following the method of standard test ASTM D 1693 method B with a solution of 10 % Igepal CO630.
  • the production rate is very high even though the melt index is low.
  • the polyethylene resin was obtained by continuous polymerisation in a loop slurry reactor with a supported and ionised metallocene catalyst prepared in two steps by first reacting SiO 2 with MAO to produce SiO 2 .MAO and then reacting 94 wt% of the SiO 2 .MAO produced in the first step with 6 wt% of ethylene bis-(tetrahydroindenyl) zirconium dichloride.
  • the dry catalyst was slurried in isobutane and pre-contacted with triisobutylaluminium (TIBAI, 10 wt% in hexane) before injection in the reactor.
  • TIBAI triisobutylaluminium
  • C2 is ethylene
  • C6 is 1-hexene
  • iC4 is isobutane
  • TIBAI is triisobutylaluminium
  • Resin R2 is a classical medium density polyethylene (MDPE) resin produced with a chromium catalyst commercialised under the name ®Finathesse HF513. It was prepared with a titanated supported chromium catalyst.
  • MDPE medium density polyethylene
  • the pipes prepared with the metallocene-produced polyethylene have a good thickness distribution. They can be produced with a low extrusion pressure, the extrusion temperature is lower than that of the pipes prepared with conventional MDPE and the extrusion output is very high.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP01202577A 2001-07-04 2001-07-05 Tubes et tuyauterie brillante Withdrawn EP1273436A1 (fr)

Priority Applications (14)

Application Number Priority Date Filing Date Title
EP01202577A EP1273436A1 (fr) 2001-07-05 2001-07-05 Tubes et tuyauterie brillante
JP2003510208A JP2004533375A (ja) 2001-07-04 2002-07-02 光沢性のチューブおよびパイプ．
AU2002354708A AU2002354708A1 (en) 2001-07-04 2002-07-02 Glossy tubes and pipes
PCT/EP2002/007491 WO2003004207A2 (fr) 2001-07-04 2002-07-02 Tubes et tuyaux brillants
DE60214189T DE60214189T2 (de) 2001-07-04 2002-07-02 Glänzende rohre und schläuche
PT02751113T PT1409245E (pt) 2001-07-04 2002-07-02 Tubos e tubagens brilhantes
US10/483,004 US20040241362A1 (en) 2001-07-04 2002-07-02 Glossy tubes and pipes
ES02751113T ES2269737T3 (es) 2001-07-04 2002-07-02 Tubos y conductos brillantes.
AT02751113T ATE337175T1 (de) 2001-07-04 2002-07-02 Glänzende rohre und schläuche
EP02751113A EP1409245B1 (fr) 2001-07-04 2002-07-02 Tubes et tuyaux brillants
DK02751113T DK1409245T3 (da) 2001-07-04 2002-07-02 Blanke tuber og rör
CNB028158016A CN100421929C (zh) 2001-07-04 2002-07-02 光泽的管子及管状物
KR1020047000006A KR100937461B1 (ko) 2001-07-04 2002-07-02 광택 튜브 및 파이프
US12/332,069 US20090136699A1 (en) 2001-07-04 2008-12-10 Glossy Tubes and Pipes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP01202577A EP1273436A1 (fr) 2001-07-05 2001-07-05 Tubes et tuyauterie brillante

Publications (1)

Publication Number Publication Date
EP1273436A1 true EP1273436A1 (fr) 2003-01-08

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EP01202577A Withdrawn EP1273436A1 (fr) 2001-07-04 2001-07-05 Tubes et tuyauterie brillante

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003031175A1 (fr) * 2001-10-02 2003-04-17 Atofina Research Recipients en plastique brillants a haute resistance a la craquelure due a la contrainte environnementale
CN109906335A (zh) * 2016-11-01 2019-06-18 艾普福流体输送用电子管有限公司 减少管中的微生物生长

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4374227A (en) * 1981-05-15 1983-02-15 Union Carbide Corporation Extruded gloss improvement in pipe blends with low pressure low density polyethylene
EP0597502A2 (fr) * 1992-11-13 1994-05-18 W.R. Grace & Co.-Conn. Films rétractables à la chaleur contenant des copolymères catalisés par cataliseurs de site singulier
US5443098A (en) * 1992-11-27 1995-08-22 Rasmussen Gmbh Thermoplastic pipe nipple
EP0687558A2 (fr) * 1994-05-19 1995-12-20 Viskase Corporation Film étirable en polyoléfine
EP0701897A2 (fr) * 1994-09-16 1996-03-20 W.R. Grace & Co.-Conn. Feuille thermoplastique multicouche pour emballer de l'eau
WO1996019527A2 (fr) * 1994-12-22 1996-06-27 Exxon Chemical Patents Inc. Articles en polyethylene a resistance amelioree a la transmission de la vapeur d'eau
EP0733472A2 (fr) * 1995-03-22 1996-09-25 W.R. Grace & Co.-Conn. Film à plusieurs couches pour l'emballage et l'administration de solutions médicales
EP0756931A2 (fr) * 1995-07-31 1997-02-05 Kureha Kagaku Kogyo Kabushiki Kaisha Feuille multicouche
US5707088A (en) * 1995-08-28 1998-01-13 Contech Construction Products, Inc. Joint for coupling plastic corrugated pipes
US6153716A (en) * 1994-06-01 2000-11-28 Phillips Petroleum Company Polyethylenes containing a unique distribution of short chain branching

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4374227A (en) * 1981-05-15 1983-02-15 Union Carbide Corporation Extruded gloss improvement in pipe blends with low pressure low density polyethylene
EP0597502A2 (fr) * 1992-11-13 1994-05-18 W.R. Grace & Co.-Conn. Films rétractables à la chaleur contenant des copolymères catalisés par cataliseurs de site singulier
US5443098A (en) * 1992-11-27 1995-08-22 Rasmussen Gmbh Thermoplastic pipe nipple
EP0687558A2 (fr) * 1994-05-19 1995-12-20 Viskase Corporation Film étirable en polyoléfine
US6153716A (en) * 1994-06-01 2000-11-28 Phillips Petroleum Company Polyethylenes containing a unique distribution of short chain branching
EP0701897A2 (fr) * 1994-09-16 1996-03-20 W.R. Grace & Co.-Conn. Feuille thermoplastique multicouche pour emballer de l'eau
WO1996019527A2 (fr) * 1994-12-22 1996-06-27 Exxon Chemical Patents Inc. Articles en polyethylene a resistance amelioree a la transmission de la vapeur d'eau
EP0733472A2 (fr) * 1995-03-22 1996-09-25 W.R. Grace & Co.-Conn. Film à plusieurs couches pour l'emballage et l'administration de solutions médicales
EP0756931A2 (fr) * 1995-07-31 1997-02-05 Kureha Kagaku Kogyo Kabushiki Kaisha Feuille multicouche
US5707088A (en) * 1995-08-28 1998-01-13 Contech Construction Products, Inc. Joint for coupling plastic corrugated pipes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003031175A1 (fr) * 2001-10-02 2003-04-17 Atofina Research Recipients en plastique brillants a haute resistance a la craquelure due a la contrainte environnementale
US7514130B2 (en) 2001-10-02 2009-04-07 Fina Technology, Inc. High ESCR glossy plastic containers
CN109906335A (zh) * 2016-11-01 2019-06-18 艾普福流体输送用电子管有限公司 减少管中的微生物生长

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